Ortho-bis(etherdianhydrides)

ABSTRACT

Disclosed herein are novel poly(imide-ethers) containing ortho substitution in the main chain of the polymer. These polymers are made from novel aromatic bis-carboxylic anhydrides which contain two ether groups attached to an aromatic ring in ortho positions to each other. The polymers are particularly useful for films, fibers and encapsulation, as well as thermoplastics.

This is a division of application Ser. No. 08/235,572, filed Apr. 29,1994, now U.S. Pat. No. 5,434,241.

FIELD OF THE INVENTION

Disclosed herein are aromatic poly(imide-ethers) which are derived fromnovel aromatic bis-carboxylic anhydrides which contain two ether groupsbonded to an aromatic ring in an ortho position.

TECHNICAL BACKGROUND

Poly(imide-ethers) are a known class of polymers, some of which are soldcommercially for use as, for instance, thermoplastics for injectionmolding parts. Therefore such polymers with particularly usefulproperties are sought by the artisan.

U.S. Pat. Nos. 3,847,867, 3,787,475, 4,769,439, and T. Takekoshi, etal., J. Poly. Sci., Poly. Symp., vol. 74, p. 93-108 (1986) describecertain poly(imide-ethers). In none of these references are polymerswith ether linkages bound ortho to each other to an aromatic ringspecifically disclosed.

U.S. Pat. No. 3,879,428 and Takekoshi, et al., (see above) describe thepreparation of certain bis-carboxylic anhydrides which also containether linkages. No such compounds are specifically described in whichether linkages are bound ortho to each other to an aromatic ring.

C. P. Yang, et al., Macromolecules, vol. 26, p. 4865 to 4871 (1993) andC. P. Yang, et al., J. Polym. Sci., Part A, vol. 32, p. 435-444 (1994)describe the synthesis of certain ortho substituted diaminoethers whichare converted into poly(imide-ethers) or poly(imide-amide-ethers).Poly(imide-ethers) from othro substituted dicarboxylic anhydrides arenot mentioned.

SUMMARY OF THE INVENTION

This invention concerns, a poly(imide-ether) which comprises the repeatunit ##STR1## wherein: Ar¹ is 1,2-naphthylene, 2,3-naphthylene or##STR2## Ar² is an arylene radical containing one or more aromaticrings; and R¹, R², R³, and R⁴ are each independently hydrogen, chlorine,fluorine, alkyl containing 1 to 10 carbon atoms, or phenyl.

This invention also concerns a compound of the formula ##STR3## wherein:Ar¹ is 1,2-naphthylene, 2,3-naphthylene or ##STR4## R¹, R², R³, and R⁴are each independently hydrogen, fluorine, chlorine, alkyl containing 1to 10 carbon atoms, or phenyl.

DETAILS OF THE INVENTION

The poly(imide-ethers) described herein are made from the novelbis-carboxylic anhydrides of formulas (IV), (V) and (VI). Thepreparation of some anhydrides of formulas (IV) and (V) are found inExamples 1 through 7, and these and other methods are also described inT. Takekoshi, et al., above. Preparation of the anhydride of formula(VI) can be done by using a mixture of 3-nitrophthalonitrile and4-nitrophthalonitrile in the reaction with catechol or a catecholderivative. As the art skilled will recognize, a mixture ofbis-carboxylic anhydrides of formulas (IV), (V) and (VI) will beobtained. These may be separated by conventional means, such asfractional crystallization. Anhydrides of formulas (IV) and (V) arepreferred.

Bis-carboxylic anhydrides with various groups other than hydrogen forR¹, R², R³ and/or R⁴ can be obtained by using procedures similar tothose in these Examples, but starting with an appropriately substitutedcatechol. All of the following preferred structures are applicable toboth the bis-carboxylic anhydrides and poly(imide-ethers) claimedherein. It is preferred if Ar¹ is substituted or unsubstituted1,2-phenylene. It is also preferred if:

R¹, R², R³, and R⁴ are hydrogen;

R¹ and R³ are hydrogen and R² and R⁴ are t-butyl;

R¹, R³ and R⁴ are hydrogen and R² is t-butyl;

R¹ is methyl and R², R³ and R⁴ are hydrogen;

R¹, R³ and R⁴ are hydrogen and R² is methyl; or

R¹ is fluorine and R², R³ and R⁴ are hydrogen.

It is also preferred if:

R¹ is alkyl and R², R³ and R⁴ are hydrogen;

R¹, R³ and R⁴ are hydrogen and R² is alkyl; or

R¹ and R³ are alkyl, and R² and R⁴ are hydrogen.

It is especially preferred if R¹, R², R³, and R⁴ are hydrogen. It ispreferred if these alkyl groups contain 1 to 4 carbon atoms.

The poly(imide-ethers) may be produced by reacting the instantbis-carboxylic anhydrides (or their precursor tetracarboxylic acids)with an aromatic diamine of the formula H₂ N-Ar² -NH₂, wherein Ar² isthe same Ar² in the formula of the poly(imide-ether) repeat unit (analternate method is the reaction of the bis-carboxylic anhydride with adiisocyanate). Ar² is an arylene radical whose two free bonds are on (orconnect to) a carbon atom of an aromatic ring. Each of these free bondsmay be to the same or different aromatic rings, and Ar² contains one ormore aromatic rings. These rings may be fused, connected by covalentbonds, and/or connected through inert groups. Suitable radicals for Ar²include 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene,3,4'-biphenylene, 3,3'-biphenylene, 2,4'-biphenylene, 2,2'-biphenylene,2,6-naphthylene, ##STR5## wherein X is alkylene, alkylidene, --S--,--O--, --C(CF₃)₂ -- and --SO₂ --, and ##STR6## wherein n is 0 or 1 and mis 0, 1 or 2, provided that each of the benzene rings is meta or parasubstituted by the bond or groups connecting the rings. Preferred groupsfor Ar² are 1,4-phenylene, 1,3-phenylene, or ##STR7##

After the bis-carboxylic anhydride is reacted with the diamine (to forma polyamic acid), the polyamic acid is converted to thepoly(imide-ether) by heating and/or chemical means. These types ofreactions are well known to the artisan, see for instance the U.S.Patents mentioned above, B. Elvers, et al., Ed., Ullamnn's Encyclopediaof Industrial Chemistry, vol. A21, VCH Verlagsgesellschaft mbH,Weinheim, 1992, p. 253-272, and Examples 17 to 45 herein.

The polymers herein may be copolymers, that is contain different Ar²groups, may be derived from more than one of the above anhydrides, ormay contain polyimide and/or poly(imide-ether) repeat units which arederived from amines and/or carboxylic anhydrides different from thosedisclosed herein.

Given the fact that the poly(imide-ethers) herein contain an orthosubstituted group (Ar¹) in the polymer chain, many of them surprisinglyhave relatively high glass transition temperatures (Tg), in some casesabout the same Tg's as the analogous meta substitutedpoly(imide-ethers), see Table 7 in the Examples. This is often combinedwith good solubility at ambient temperatures in common organic solvents(the analogous meta and para substituted polymers are often much lesssoluble under these conditions), making the instant polymersparticularly useful for coatings, fibers, films and for encapsulationresins. Certain of the instant polymers may also be used for typicalthermoplastic uses, such as molding parts or for wire insulation. Someof these polyimides are also colorless.

EXAMPLE 1

Preparation of 1,2-bis-(3,4-dicyanophenoxy) benzene

51.9 g (0.3 moles) of 4-nitrophthalonitrile was dissolved in 200 mlanhydrous dimethyl sulphoxide (DMSO) in a 500 ml three-necked flaskfitted with a stirrer, nitrogen-gas inlet and thermometer. 16.5 g (0.15moles) of catechol (supplied by Aldrich) was added to the mixturefollowed by 23 g of anhydrous potassium carbonate. The mixture wasstirred at room temperature with a stream of dry, oxygen-free nitrogenpassing through the flask for 20 hours. After that time an additional 2g (0.011 moles) of 4-nitrophthalonitrile was added, followed by 16 gpotassium carbonate and the mixture stirred for an additional 6 hours.The reaction mixture was then poured into 3 1 of water to produce asolid product which was washed five times with water and three timeswith methanol. The product (50 g, 92.1% yield) in the form of a whitepowder was recrystallised from acetonitrile to yield white crystals of1,2-bis-(3,4-dicyanophenoxy) benzene having the formula: ##STR8## Themelting point of this product was 190.1°-190.6° C. Elemental analysis ofC₂₂ H₁₀ N₄ O₂ was calc.: C, 72.92%; H, 2.76%; N, 15.67%; found: C,72.83%; H, 2.76%; N, 15.57%.

EXAMPLE 2

Preparation of 1,2-bis-(2,3-dicyanophenoxy) benzene

The same apparatus as was used in Example 1 was also used in thisexample. 3 g (0.0173 moles) of 3-nitrophthalonitrile, was dissolved in15 ml of anhydrous dimethyl sulphoxide in the three-necked flask. 0.95 g(0.00863 moles) of catechol and 2 g of potassium carbonate were added tothe reaction mixture. The mixture was stirred at room temperature with astream of dry, oxygen-free nitrogen passing through the flask for 26hours. The product was isolated by pouring the reaction mixture into 300ml of water. The resultant solid precipitate was filtered and washeduntil the effluent was neutral. The product (which was an off-whitepowder) was recrystallized from methanol/acetonitrile (20/80) to yieldoff-white crystals of 1,2-bis-(2,3-dicyanophenoxy) benzene having theformula: ##STR9## The melting point was 158°-159° C. The elementalanalysis for C₂₂ H₁₀ N₄ O₂ was calc.: C, 72.92%; H, 2.76%; N, 15.67%;found: C, 72.57%; H, 2.72%; N, 15.43%.

EXAMPLE 3

Preparation of 1,2-bis-(3,4-dicyanophenoxy)-3,5-ditertiarybutylbenzene

3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile wasdissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fittedwith a magnetic stirrer bar, nitrogen-gas inlet and thermometer. 2.22 g(0.01 moles) of 3,5-ditertiarybutylcatechol (supplied by Fluka) wasadded to the mixture followed by 5 g of anhydrous potassium carbonate.The mixture was stirred at room temperature for 24 hours and the mixturewas precipitated into 400 ml water. The white solid product was washedthree times with water and a further three times with methanol to yield4.70 g (99.1% of theoretical yield) of a snow-white product which wasfurther recrystallized from acetonitrile to yield 4.1 g of product withthe formula: ##STR10## The melting point of this product was 247°-248°C. The elemental analysis for C₃₀ H₂₆ N₄ O₂ was calc.: C, 75.94%; H,5.48%; N, 11.81%; found: C, 76.07%; H, 5.51%; N, 11.86%.

EXAMPLE 4

Preparation of 2,3-bis-(3,4-dicyanophenoxy)naphthalene

3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile wasdissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fittedwith a magnetic stirrer bar, nitrogen-gas inlet and thermometer. 1.60 g(0.01 moles) of 2,3-dihydroxynaphthalene (supplied by Aldrich) was addedto the mixture followed by 5 g of anhydrous potassium carbonate. Thereaction mixture was stirred at room temperature for 24 hours and thenpoured into 500 ml water. The off-white product was filtered off andwashed with water until the washings were neutral, and then withmethanol to yield 4.12 g (99.2% of theoretical yield) of crudetetranitrile which was further recrystallized from 240 ml acetonitrile.The product had the formula: ##STR11## and a melting point of 265°-266°C. The elemental analysis for C₂₆ H₁₂ N₄ O₂ was calc.: C, 75.72%; H,2.91%; N, 13.59%; found: C, 75.50%; H, 2.89%; N, 13.51%.

EXAMPLE 5

Preparation of 1,2-bis-(3,4-dicyanophenoxy)-3-methylbenzene

3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile wasdissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fittedwith a magnetic stirrer bar under nitrogen. 1.24 g (0.01 moles) of3-methylcatechol (Aldrich) was added to the mixture followed by 5 g ofanhydrous potassium carbonate. The reaction mixture was stirred at roomtemperature for 24 hours and then precipitated into 400 ml water. Theyellow solid was washed with water until the washings were neutral. Thewet product was recrystallized twice from methanol/acetonitrile (4:1) toyield 2.80 g of pure white tetranitrile and 0.35 g of a less pureproduct (83.8% theoretical yield). The product had the formula:##STR12## The melting point was 194.3°-195.3° C. The elemental analysisfor C₂₃ H₁₂ N₄ O₂ was calc.: C, 73.40%; H, 3.19%; N, 14.89%; found: C,73.38%; H, 3.16%; N, 14.95%.

EXAMPLE 6

Preparation of 1,2-bis-(3,4-dicyanophenoxy)-4-methylbenzene

3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile wasdissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fittedwith a magnetic stirrer bar under nitrogen. 1.24 g (0.01 moles) of4-methylcatechol (Aldrich) was added to the mixture followed by 5 g ofanhydrous potassium carbonate. The mixture was stirred at roomtemperature for 24 hours. The workup was as described in Example 5 andyielded 3.08 g of off-white crystals of the title compound (81.2%theoretical yield). The product had the formula: ##STR13## The meltingpoint was 194°-195° C. The elemental analysis for C₂₃ H₁₂ N₄ O₂ wascalc.: C, 73.40%; H, 3.19%; N, 14.89%; found: C, 73.31%; H, 3.15%; N,14.99%.

EXAMPLE 7

Preparation of 1,2-bis-(3,4-dicyanophenoxy)-4-tert-butylbenzene

The experimental procedure and reaction conditions were the same asdescribed for Examples 5 and 6. Reagents used were 3.60 g (0.02 molesplus 0.14 g excess) of 4-nitrophthalonitrile and 1.66 g (0.01 moles) of4-tert-butylcatechol (Aldrich). After workup and recrystallization 3.2 g(76.55% theoretical yield) of off-white crystals of the title compoundwere obtained. The product had the formula: ##STR14## The melting pointwas 161°-162° C. The elemental analysis for C₂₆ H₁₈ N₄ O₂ was calc.: C,74.64%; H, 4.30%; N, 13.39%; found: C, 74.55%; H, 4.25%; N, 13.39%.

EXAMPLE 8

Preparation of 1,2-bis-(3,4-dicyanophenoxy)-3-fluorobenzene

3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile wasdissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fittedwith a magnetic stirrer bar under nitrogen. 1.28 g (0.01 moles) of3-fluorocatechol (Aldrich) was added to the mixture followed by 5 g ofanhydrous potassium carbonate. The mixture was stirred at roomtemperature for 24 hours. The workup was as described in Example 5 andyielded 3.04 g of off-white crystals of the title compound (80%theoretical yield). The product had the formula: ##STR15## The meltingpoint was 198.5°-199.5° C. The elemental analysis for C₂₂ H₉ FN₄ O₂ wascalc.: C, 69.47%; H, 2.36%; N, 14.73%; found: C, 69.47%; H, 2.34%; N,14.80%.

EXAMPLE 9

General procedure for the hydrolysis of1,2-bis(3,4-cyanophenoxy)benzenes

0.1 moles of a 1,2-bis(3,4-cyanophenoxy)benzene (tetranitrile) wassuspended in 100 g of a 50 wt % aqueous solution of potassium hydroxide.Then 100 ml (or more if needed to wet the solid) of methanol was added.The mixture was boiled under reflux. Within the first 2-4 hours, thesolid tetranitrile dissolved. The reflux was continued until theevolution of ammonia has ceased. The solution was then diluted withdeionized water to 1.5-2 liters and acidified with concentratedhydrochloric acid to a pH of 1.5-2. The solid tetraaccid was filteredoff and washed with deionized water until neutral and no chloride ionscould be detected. Then the tetraacid product with formula: ##STR16##was dried. Yields were generally in the range 92-98% of theoretical,products were not characterized in detail. Acids synthesized from theteranitriles cited in Examples 1 to 9 are listed in Table 1.

EXAMPLE 10

Preparation of 1,2-bis(3,4-dicarboxyphenoxy)benzene dianhydride

53.9 g (0.123 moles) of 1,2-bis-(3,4-dicarboxyphenoxy)benzene (Example9a), prepared from the corresponding tetranitrile (Example 1) asdescribed in Example 9, was suspended in 300 ml of warm glacial aceticacid and 300 ml of acetic anhydride was added. The mixture was boiledunder reflux for 30 min. and left to crystallize overnight. Therecovered needles of crystalline bisanhydride were recrystallized from200 ml of acetic anhydride to yield 41 g of off-white long needles ofthe anhydride with the formula: ##STR17## which had a melting point of187.1°-187.6° C. The elemental analysis for C₂₂ H₁₀ O₈ was calc.: C,65.67%; H, 2,48%; found: C, 65.69%; H, 2.45%,

EXAMPLE 11

Preparation of 1,2-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride

3.47 g (0.007 moles) of 2,3-bis-(3,4-dicarboxyphenoxy)naphthalene(Example 9h), synthesized according to the procedure described inExample 9 from the tetranitrile synthesized in Example 4, was suspendedin 15 ml of acetic acid and brought to the boil, 100 ml of aceticanhydride was added in aliquots and the mixture boiled gently for 40min. After leaving overnight to cool the white crystals whichprecipitated were filtered off and dried in a vacuum oven at 140° C. toyield 3.05 g (95% of theoretical yield) of the bisanhydride having theformula: ##STR18## with a melting point of 264.6°-265.4° C. Theelemental analysis for C₂₆ H₁₂ O₈ was calc.: C, 69.02%; H, 2.65%; found:C, 68.95%; H, 2.57%.

EXAMPLE 12

Preparation of 1,2-bis-(3,4-dicarboxyphenoxy)-3,5-ditertiarybutylbenzenedianhydride

The tetranitrile described in Example 3, after hydrolysis (Example 9f)was converted into the title anhydride using the same procedure as thatdescribed in Example 10. The anhydride, with formula ##STR19## wasrecrystallized from acetonitrile/acetic anhydride (6:1 v/v). Analyticaldata, yield and melting point are given in Table 2.

EXAMPLE 13

Preparation of 1,2-bis-(3,4-dicarboxyphenoxy)-3-methylbenzenedianhydride

The product tetranitrile from Example 5, after hydrolysis (Example 9c),was converted to the title dianhydride using the procedure described inExample 10. The dianhydride of formula ##STR20## was recrystallized fromacetonitrile/acetic anhydride (1:1 v/v). Analytical data, yield andmelting point are given in Table 2.

EXAMPLE 14

Preparation of 1,2-bis-(3,4-dicarboxyphenoxy)-4-methylbenzenedianhydride

The product tetranitrile from Example 6, after hydrolysis (Example 9d),was converted to the title dianhydride using the procedure described inExample.10. The dianhydride of formula ##STR21## was recrystallized fromacetonitrile/acetic anhydride (3:1 v/v). Analytical data, yield andmelting point are given in Table 2.

EXAMPLE 15

Preparation of 1,2-bis-(3,4-dicarboxyphenoxy)-4-tert-butylbenzenedianhydride

The product tetranitrile from Example 7, after hydrolysis (Example 9e),was converted to the title dianhydride using the procedure described inExample 10. The dianhydride of formula ##STR22## was recrystallized fromacetonitrile/acetic anhydride (9:1 v/v). Analytical data, yield andmelting point are given in Table 2.

EXAMPLE 16

Preparation of 1,2-bis-(3,4-dicarboxyphenoxy)-3-fluorobenzenedianhydride

The product tetranitrile from Example 8, after hydrolysis (Example 9g),was converted to the title dianhydride using the procedure described inExample 10. The dianhydride of formula ##STR23## was recrystallized fromacetonitrile/acetic anhydride (10:1 v/v). Analytical data, yield andmelting point are given in Table 2.

POLYMER SYNTHESES

Poly(ether imide)s derived from the catechol-based dianhydridessynthesized in Examples 10-16 were all synthesized by a common proceduredescribed in full in Example 17; any variations are cited in thespecific example. The diamines used in the several syntheses areidentified by a code in the titles of the Examples and by theirstructural formulae in Table 3. The characterization details of thepolymers and copolymers prepared are given in Tables 4 and 5 and inthese and other tables the dianhydrides used are identified by a codegiven with the systematic names of the anhydrides in Examples 17-45.

EXAMPLE 17

Preparation of polymer from 1,2-bis(3,4-carboxphenoxy)benzenedianhydride (CBA) and m-Phenylene Diamine (MPD)

2.702 g (0.025 moles) of sublimed m-phenylene diamine (Fluka) wasdissolved in 100 ml of anhydrous dimethyl acetamide (DMAC) in a flaskfitted with a magnetic stirrer bar. 10.05 g (0.025 moles) of1,2-bis(3,4-carboxyphenoxy) benzene dianhydride (CBA) (synthesized inExample 10 from the tetranitrile synthesized in Example 1 and anhydridein Example 9a) was added, in one portion, with stirring at roomtemperature. After 20 hours the viscous solution was imidized with 40 mlof a 50:50 mixure of acetic anhydride and pyridine. The mixture wasallowed to stand, with stirring, for 6 hours. The mixture was thenprecipitated into 4 l of methanol and was boiled in methanol to removeresidual solvent. The polymer was filtered off and dried, redissolved in100 ml of chloroform and reprecipitated. The final yield was 11.9 g of awhite polymer soluble in chlorinated hydrocarbons (CH₂ Cl₂, CHCl₃),DMAC, NMP and cresol. The polymer had molecular weights M_(n) =11,700,M_(w) =44,000 and M_(peak) =62,000 g mol⁻¹, determined by gel permeationchromatography. The glass-transition temperature of the polymer is givenin Table 4. When molten at 360° C. long fibres could be pulled from themelt.

EXAMPLE 18

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and p-Phenylene diamine (PPD)

The polymer was prepared from 0.001 moles of PPD (Aldrich Chem. Co.) and0.001 moles of CBA according to the procedure described in Example 17except that the polymer precipitated on imidization. The product wasboiled in methanol; details of the product are given in Table 4.

EXAMPLE 19

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and 4,4'-diaminophenyl ether (ODA)

0.200 g (0.001 moles) of 4,4'-diaminophenyl ether (ultra pure, ex BP)was dissolved in 5 ml of anhydrous DMAC in a flask fitted with amagnetic stirrer bar. 0.402 g (0.001 moles) of1,2-bis(3,4-carboxyphenoxy)benzene dianhydride (synthesized according toExample 11) was added, in one portion, with stirring at roomtemperature. After 20 hours the viscous solution was imidized with 1.4ml of a 50:50 mixure of acetic anhydride and pyridine, to yield 0.56 gof a lemon-coloured polymer soluble in chlorinated hydrocarbons (CH₂Cl₂, CHCl₃), DMAC, NMP and cresol. The polymer had a glass-transitiontemperature of 208° C.

EXAMPLE 20

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and 3,4'-diaminophenyl ether (3,4-ODA)

The polymer was prepared from 0.001 moles of 3,4-ODA (Kennedy and Klim)and 0.001 moles of CBA according to the procedure described in Example17; details of the product are given in Table 4.

EXAMPLE 21

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and TPE-Q

The polymer was prepared from 0.001 moles of TPE-Q (Kennedy and Klim)and 0.001 moles of CBA according to the procedure described in Example17. After three hours imidization the polymer formed a gel which wasextracted by boiling with methanol; details of the product are given inTable 4.

EXAMPLE 22

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and TPE-R

The polymer was prepared from 0.001 moles of TPE-R (Kennedy and Klim)and 0.001 moles of CBA according to the procedure described in Example17. After three hours imidization the system formed into an opaque gelwhich was extracted by boiling with methanol; details of the product aregiven in Table 4.

EXAMPLE 23

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) End BAPB

The polymer was prepared from 0.001 moles of BAPB (Kennedy and Klim) and0.001 moles of CBA according to the procedure described in Example 17.After imidizing for two hours the polymer precipitated and was washedwith boiling methanol; details of the product are given in Table 4.

EXAMPLE 24

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and tetramethylphenylene diamine (TMpPD)

The polymer was prepared from 0.001 moles of TMpPD (Aldrich Chem. Co.)and 0.001 moles of CBA according to the procedure described in Example17. The polymer remained in solution on imidization; details of theproduct are given in Table 4.

EXAMPLE 25

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxyl benzenedianhydride (CBA) and 3,3',5,5'-tetramethylbenzidine (TMB)

0.243 g (0.001 moles) of 3,3',5,5'-tetramethylbenzidine (Aldrich Chem.Co. ) was dissolved in 5 ml of anhydrous DMAC in a flask fitted with amagnetic stirrer bar. 0.402 g (0.001-moles) of1,2-bis(3,4-carboxyphenoxy)benzene dianhydride was added, in oneportion, with stirring at room temperature. After 20 hours the viscousSolution was imidized with 1.4 ml of a 50:50 mixure of acetic anhydrideand pyridine to yield 0.60 g of a polymer soluble in chlorinatedhydrocarbons CHCl₃, DMAC, NMP and cresol.

EXAMPLE 26

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and BAP

The polymer was prepared from 0.001 moles of BAP (Kennedy and Klim Inc.) and 0.001 moles of CBA according to the procedure described in Example17; details of the product are given in Table 4.

EXAMPLE 27

Preparation of polymer from 1,2-bis (3,4-carboxyphenoxy)benzenedianhydride (CBA) and BAAF

The polymer was prepared from 0.001 moles of BAAF (British Petroleum)and 0.001 moles of CBA according to the procedure described in Example17; details of the product are given in Table 4.

EXAMPLE 28

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and MBXD

The polymer was prepared from 0.001 moles of MBXD (Kennedy and Klim Inc.) and 0.001 moles of CBA according to the procedure described in Example17; details of the product are given in Table 4.

EXAMPLE 29

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy(benzenedianhydride (CBA) and DApTP

The polymer was prepared from 0.001 moles of DApTP (Lancaster Synthesis)and 0.001 moles of CBA according to the procedure described in Example17. During imidization the polymer precipitated out as an opaque gel;details of the product are given in Table 4.

EXAMPLE 30

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)-3-methylbenzenedianhydride (3-MCBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of3-MCBA (synthesized as in Example 13 from the tetranitrile synthesizedin Example 5 and hydrolysed according to the procedure in Example 10)according to the procedure described in Example 17; details of theproduct are given in Table 4.

EXAMPLE 31

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)-4-methylbenzenedianhydride (4-MCBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of4-MCBA (synthesized as in Example 14 from the tetranitrile synthesizedin Example 6 and hydrolysed according to the procedure in Example 10)according to the procedure described in Example 17; details of theproduct are given in Table 4.

EXAMPLE 32

Preparation of polymer from1,2-bis(3,4-carboxyphenoxy)-4-tert-butylbenzene dianhydride (4-tBCBA)add ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of4-tBCBA (synthesized as in Example 15 from the tetranitrile synthesizedin Example 7 and hydrolysed according to the procedure in Example 10)according to the procedure described in Example 17; details of theproduct are given in Table 4.

EXAMPLE 33

Preparation of polymer from1,2-bis(3,4-carboxyphenoxy)-3,5-ditert-butylbenzene dianhydride(3,5-tBCBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of3,5-tBCBA (synthesized as in Example 12 from the tetranitrilesynthesized in Example 6 and hydrolysed according to the procedure inExample 3) according to the procedure described in Example 17; detailsof the product are given in Table 4.

EXAMPLE 34

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)-3-fluorobenzenedianhydride (3-(CBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of3-FCBA (synthesized as in Example 16 from the tetranitrile synthesizedin Example 6 and hydrolysed according to the procedure in Example 8)according to the procedure described in Example 17; details of theproduct are given in Table 4.

EXAMPLE 35

Preparation of polymer from 2,3-bis(3,4-carboxyphenoxy) naphthalenedianhydride (2,3-NBA) and ODA

The polymer was prepared from 0.001 moles of 2,3-NBA and 0.001 moles of2,3-NBA (synthesized as in Example 11 from the tetranitrile synthesizedin Example 6 and hydrolysed according to the procedure in Example 4)according to the procedure described in Example 17; details of theproduct are given in Table 4.

EXAMPLE 36

Preparation of polymer from (1,2-bis(3,4-carboxyphenoxy)-3-methylbenzenedianhydride (3-MCBA) and MPD

The polymer was prepared from 0.001 moles of MPD and 0.001 moles of3-MCBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 37

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy-3-methylbenzenedianhydride (3-MCBA) and TPE-Q

The polymer Was prepared from 0.001 moles of TPE-Q and 0.001 moles of3-MCBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 38

Preparation of polymer from 1,2-bis(3,4-carboxyphenoxy)-4-methylbenzenedianhydride (4-MCBA) and TPE-Q

The polymer was prepared from 0.001 moles of TPE-Q and 0.001 moles of4-MCBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 39

Preparation of polymer from1,2-bis(3,4-carboxyphenoxy)-3,5-ditert-butylbenzene dianhydride(3,5-tBCBA) and PPD

The polymer was prepared from 0.001 moles of PPD and 0.001 moles of3,5-tBCBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 40

Preparation of polymer from 2,3-bis(3,4-carboxyphenoxy)naphthalenedianhydride (2,3-NBA) and MPD

The polymer was prepared from 0.001 moles of MPD and 0.001 moles of2,3-NBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 41

Preparation of polymer from 2,3-bis(3,4-carboxy-phenoxy)naphthalenedianhydride (2,3-NBA) and BAPB

The polymer was prepared from 0.001 moles of BAPB and 0.001 moles of2,3-NBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 42

Preparation of polymer from 2,3-bis (3,4-carboxyphenoxy)naphthalenedianhydride (2,3-NBA) and MBXD

The polymer was prepared from 0.001 moles of MBXD and 0.001 moles of2,3-NBA according to the procedure described in Example 17; details ofthe product are given in Table 4.

EXAMPLE 43

Preparation of copolymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and MPD (0.9) and PPD (0.1)

0.0225 moles of MPD and 0.0025 moles of PPD were dissolved together in100 ml of anhydrous dimethyl acetamide (DMAC) in a flask fitted with amagnetic stirrer bar. 0.025 moles of CBA was added, in one portion, withstirring at room temperature. After 20 hours the viscous solution wasimidized and the copolymer recovered as described in Example 10.

EXAMPLE 44

Preparation of copolymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and MPD (0.7) and PPD (0.3)

A copolymer was prepared from 0.0175 moles of MPD, 0.0075 moles of PPDand 0.025 moles of CBA according to the procedure described in Example43. After one hour imidization the system formed into a gel.

EXAMPLE 45

Preparation of copolymer from 1,2-bis(3,4-carboxyphenoxy)benzenedianhydride (CBA) and MPD (0.5) and PPD (0.5)

A copolymer was prepared from 0.0125 moles of MPD, 0.0125 moles of PPDand 0.025 moles of CBA according to the procedure described in Example43. A gel formed after one hour of imidization.

COMPARATIVE POLYMERS

For comparative purposes samples of bis(ether anhydride) s HBA and RBAwere prepared from hydroquinone and resorcinol, respectively, followingthe above procedures. First the tetranitriles were prepared bynitrodisplacement with 4-nitrophthalonitrile using the same proceduresas that described in Example 1. The tetranitriles were then converted totetraacids and hence to the anhydrides according to Examples 9 and 10.Analytical data for the tetranitriles and anhydrides were consistentwith theory and with data reported previously by Takekoshi (T.Takekoshi, J. Polym. Sci., Polym. Symp., 1986 74 93). Polymers preparedfrom the anhydrides are described in the following comparative examples.##STR24##

COMPARATIVE EXAMPLE A

Preparation of polymer from 1,4-bis(3,4-carboxyphenoxy)benzenedianhydride (HBA) and MPD

The polymer was prepared from 0.001 moles of MPD and 0.001 moles of HBAaccording to the procedure described in Example 17. During imidizationthe polymer formed a lump of gel and was extracted by boiling withmethanol; details of the product are given in Table 5.

COMPARATIVE EXAMPLE B

Preparation of polymer from 1,3-bis(3,4-carboxyphenoxy)benzenedianhydride (RBA) and MPD

The polymer was prepared from 0.001 moles of MPD and 0.001 moles of RBAaccording to the procedure described in Example 17. During imidizationthe polymer precipitated out and was extracted by boiling with methanol;details of the product are given in Table 5.

COMPARATIVE EXAMPLE C

Preparation of polymer from 1,4-bis(3,4-carboxyphenoxy)benzenedianhydride (HBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of HBAaccording to the procedure described in Comparative Example B. Thepolymer precipitated out on imidization and was extracted by boilingwith methanol; details of the product are given in Table 5.

COMPARATIVE EXAMPLE D

Preparation of polymer from 1,3-bis(3,4-carboxyphenoxy)benzenedianhydride (RBA) and ODA

The polymer was prepared from 0.001 moles of ODA and 0.001 moles of RBAaccording to the procedure described in Comparative Example B; detailsof the product are given in Table 5.

COMPARATIVE EXAMPLE E

Preparation of low-molecular-weight polymer from1,4-bis(3,4-carboxyphenoxy)benzene dianhydride (HBA) and MPD

The polymer was prepared from 0.025 moles of MPD and 0.02375 moles ofHBA according to the procedure described in Comparative Example B exceptthat the polymer remained in solution on imidization and was extractedas in Example 1. Details of the product are given in Table 5. Thestoichiometric imbalance was used in order to produce a polymer of lowermolecular weight in order to try to produce a polymer of greatersolubility according to the standard principles of step polymerization.

COMPARATIVE EXAMPLE F

Preparation of polymer from 1,4-bis(3,4-carboxyphenoxy)benzenedianhydride (HBA) and TPE-R

The polymer was prepared from 0.001 moles of TPE-R and 0.001 moles ofHBA according to the procedure described in Comparative Example B;details of the product are given in Table 5.

COMPARATIVE EXAMPLE G

Preparation of polymer from 1,4-bis(3,4-carboxyphenoxy)benzenedianhydride (HBA) and TPE-R

The polymer was prepared from 0.001 moles of TPE-R and 0.001 moles ofRBA according to the procedure described in Comparative Example B;details of the product are given in Table 5.

COMPARATIVE EXAMPLE H

Preparation of polymer from 1,4-bis(3,4-carboxyphenoxy)benzenedianhydride (HBA) and BAPB

The polymer was prepared from 0.001 moles of BAPB and 0.001 moles of2,3-NBA according to the procedure described in Comparative Example B;details of the product are given in Table 5.

POLYMER MOLECULAR WEIGHTS

Molecular weights were determined by gel permeation chromatography usingN,N-dimethyl formamide containing 1 molar lithium chloride as eluant anda polystyrene calibration. The molecular weights quoted as M_(peak) arethe molecular weights at the peak of the gel permeation chromatogramsfor the polymers cited

POLYMER SOLUBILITIES AND GLASS-TRANSITION TEMPERATURES

The solubilities of the polymers were determined in chloroform,N,N-dimethylformamide (DMF), dimethylacetamide (DMAC),N-methylpyrollidinone (NMP) and cresol. Solvent powers increased in theorder

    chloroform<DMF<DMAC<NMP<cresol

and in defining the polymer solubilities in the Tables the symbol srefers to solubility in all solvents used and if a single solvent isspecified the polymer cited was soluble in that solvent at roomtemperature and in more powerful solvents according to the above order.

Glass-transition temperatures were determined on a Perkin Elmer DSC2.The temperatures determined in this work were transition onsettemperatures.

The solubilities and glass-transition temperatures of some polymersbased on CBA are compared with those of the corresponding polymers basedon HBA and RBA with the same diamines. The data are presented in Tables4 and 5 and are collected in Table 7.

THERMAL STABILITY

Thermal stabilities of some polymers were determined bythermogravimetric analysis. Measurements were made with the aid of aPerkin Elmer TGA7. The results are presented in Table 6.

                  TABLE 1                                                         ______________________________________                                        Tetraacids Prepared from                                                      Corresponding Tetranitriles in Examples 1 to 9                                Example                                                                              Acid                                                                   ______________________________________                                        9a                                                                                    ##STR25##                                                             9b                                                                                    ##STR26##                                                             9c                                                                                    ##STR27##                                                             9d                                                                                    ##STR28##                                                             9e                                                                                    ##STR29##                                                             9f                                                                                    ##STR30##                                                             9g                                                                                    ##STR31##                                                             9h                                                                                    ##STR32##                                                             ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Characterization Data for Dianhydrides Based on Catechcols                    Elemental Analysis                                                            Example        Calc.  Found   Yield/%                                                                             Melting Point °C.                  ______________________________________                                        12     C       70.03  69.93   89.6  147-148                                          H       5.05   5.25                                                    13     C       66.3   66.28   95.7  208-209                                          H       2.8    2.84                                                    14     C       66.3   66.44   87.7  179-180                                          H       2.8    2.81                                                    15     C       68.12  68.10   86.1  158-159                                          H       3.93   3.90                                                    16     C       62.86  62.48    85.43                                                                              177-178                                          H       2.15   2.57                                                    ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Diamines Used in Polymer Syntheses                                            Code    Structure                                                             ______________________________________                                        MPD                                                                                    ##STR33##                                                            PPD                                                                                    ##STR34##                                                            TMpPD                                                                                  ##STR35##                                                            ODA                                                                                    ##STR36##                                                            3,4-ODA                                                                                ##STR37##                                                            TMB                                                                                    ##STR38##                                                            BAAF                                                                                   ##STR39##                                                            TPE-Q                                                                                  ##STR40##                                                            TPE-R                                                                                  ##STR41##                                                            BAPB                                                                                   ##STR42##                                                            BAP                                                                                    ##STR43##                                                            MBXD                                                                                   ##STR44##                                                            DApTP                                                                                  ##STR45##                                                            ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Characteristics of Polymers                                                   Ex-                                                                           am-                                                                           ple  Anhydride Diamine  M.Wt/kg mol-1                                                                          Tg/°C.                                                                        Solubility                            ______________________________________                                        17   CBA       MPD      112      220    s                                     18   CBA       PPD      --       None   Insol                                 19   CBA       ODA      287      208    s                                     20   CBA       3,4-ODA  151      190    s                                     21   CBA       TPR-Q    --       192    cresol                                22   CBA       TPE-R    --       184    NMP                                   23   CBA       BAPB     476      204    s                                     24   CBA       TMpPD     40      --     s                                     25   CBA       TMB      --       262, 301                                                                             s                                     26   CBA       BAP      422      211    s                                     27   CBA       BAAF      62      228    s                                     28   CBA       MBXD     214      243    s                                     29   CBA       DApTP    --       No Tg  insol                                 30   3-MCBA    ODA      --       209    s                                     31   4-MCBA    ODA      --       213    s                                     32   4-tBCBA   ODA       43      205    s                                     33   3,5-tBCBA ODA      --       228    s                                     34   3-FCBA    ODA      235      214    s                                     35   2,3-NBA   ODA       36      230    S                                     36   3-MCBA    MPD      --       222    s                                     37   3-MCBA    TPE-Q    --       202    s                                     38   4-MCBA    TPE-Q    --       194    s                                     39   3,5-tCBA  PPD       31      256    s                                     40   2,3-NBA   MPD      --       230    s                                     41   2,3-NBA   BAPB     127      227    s                                     42   2,3-NBA   MBXD      97      265    s                                     43   CBA       MPD (0.9)                                                                              --       --     s                                                    PPD (0.1)                                                      44   CBA       MPD (0.7)                                                                               19      213    NMP                                                  PPD (0.3)                                                      45   CBA       MPD (0.5)                                                                              --       --     insoluble                                            PPD (0.5)                                                      ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Comparative Examples                                                          Exam-                                                                         ple   Anhydride                                                                              Diamine  M.Wt/kg mol-1                                                                          Tg/°C.                                                                        Solubility                            ______________________________________                                        A     HBA      MPD               244.sup.a                                                                            NMP.sup.a,b,c                                                          255.sup.b                                                                     242.sup.c                                    B     RBA      MPD               224.sup.b                                                                            NMP                                   C     HBA      ODA               233, 239.sup.a                                                                       NMP                                                                    237.sup.b                                    D     RBA      ODA               209.sup.b                                                                            NMP                                                                           (swells)                              E     HBA      MPD      30                                                    F     HBA      TPE-R             199.sup.b                                                                            NMP                                                                           insoluble                             G     RBA      TPE-R             188.sup.b                                                                            NMP                                                                           (swells)                              H     HBA      BAPB                     cresol                                ______________________________________                                         .sup.a Data determined in this work                                           .sup.b Data taken from the paper by T. Takekoshi, J. Polym. Sci., Polym.      Symp. 1986 74 93                                                              .sup.c Data taken from paper by M. Davies, J. N. Hay and B. Woodfine, Hig     Performance Polymers, 1993 5 37                                          

                  TABLE 6                                                         ______________________________________                                        Thermal Stability                                                                                                   Temperature                                                                   for 5%                                          Anhy-           Weight                                                                              Temperature                                                                           Weight Loss/                            Sample  dride   Amine   Loss/%                                                                              Range/°C.                                                                      °C.                              ______________________________________                                        Example 17                                                                            CBA     MPD     98.5  477-670 --                                      Comparative                                                                           HBA     MPD     97    527-682 526.sup.a                               Example A                                                                     Example 23                                                                            CBA     BAPB    100   520-676 --                                      ______________________________________                                         .sup.a Data taken from the paper by T. Takekoshi, J. Polym. Sci., Polym.      Symp., 1986 74 93                                                        

                                      TABLE 7                                     __________________________________________________________________________    Comparison of Thermal Properties and Solubilities of Polymers Based on        CBA, HBA and RBA and Several Amines                                           HBA               RBA         CBA                                             __________________________________________________________________________    MPD Comparative Example A                                                                       Comparative Example B                                                                     Example 17                                          Tg/°C. = 244.sup.a ; 2.55.sup.b ; 242/244.sup.c                                      Tg/°C. = 224.sup.b                                                                 Tg/°C. = 220.sup.a                           solubility: cresol.sup.a ; NMP.sup.b                                                        solubility: cresol.sup.a ; NMP.sup.b                                                      solubility: chloroform.sup.a                    ODA Comparative Example C                                                                       Comparative Example D                                                                     Example 19                                          Tg/°C. = 233, 239.sup.a ; 237.sup.b                                                  Tg/°C. = 209.sup.b                                                                 Tg/°C. = 208.sup.a                           solubility: cresol.sup.a ; NMP.sup.b                                                        solubility: cresol.sup.a                                                                  solubility: chloroform.sup.a                    BAPB                                                                              Comparative Example H     Example 23                                          solubility: insoluble.sup.a                                                                             Tg/°C. = 204.sup.a                                                     solubility: chloroform.sup.a                    TPE-R                                                                             Comparative Example F                                                                       Comparative Example G                                                                     Example 22                                          Tg/°C. = 199, T.sub.m /°C. = 330.sup.b                                        Tg/°C. = 199.sup.b                                                                 Tg/°C. = 184.sup.a                           solubility: insoluble.sup.b                                                                 solubility: swells in NMP.sup.b                                                           solubility: NMP.sup.a                           __________________________________________________________________________     .sup.a Data obtained in this work                                             .sup.b Data taken from the paper by T. Takekoshi, J. Polym. Sci., Polym.      Symp., 1986 74 93                                                             .sup.c Data taken from paper by M. Davies, J. N. Hay and B. Woodfine, Hig     Performance Polymers, 1993 5 37                                          

What is claimed is:
 1. A compound of the formula ##STR46## wherein: Ar¹is 1,2-naphthylene, 2,3-naphthylene or ##STR47## and R¹, R², R³, and R⁴are each independently hydrogen, fluorine, chlorine, alkyl containing 1to 10 carbon atoms, or phenyl.
 2. The compound as recited in claim 1wherein said formula is (IV) or (V).
 3. The compound as recited in claim2 wherein Ar¹ is ##STR48##
 4. The compound as recited in claim 3wherein:R¹, R², R³, and R⁴ are hydrogen; R¹ and R³ are hydrogen and R²and R⁴ are t-butyl; R¹, R³ and R⁴ are hydrogen and R² is t-butyl; R¹ ismethyl and R², R³ and R⁴ are hydrogen; R¹, R³ and R⁴ are hydrogen and R²is methyl; or R¹ is fluorine and R², R³ and R⁴ are hydrogen.
 5. Thecompound as recited in claim 3 wherein:R¹ is alkyl and R², R³ and R⁴ arehydrogen; R¹, R³ and R⁴ are hydrogen and R² is alkyl; or R¹ and R³ arealkyl, and R² and R⁴ are hydrogen.
 6. The compound as recited in claim 3wherein R¹, R², R³, and R⁴ are hydrogen.